DE102014112822B4 - Coated glass sheet and process for its manufacture - Google Patents

Abstract

Coated glass pane, comprising - a glass substrate (1), - a layer sequence (2) applied to the glass substrate (1) and composed of several inorganic layers (21, 22, 23) and - a temporary organic protective coating (3), which has a thickness between 0 , 3 nm and 500 nm, the temporary organic protective coating (3) containing a water-soluble or water-dispersible hydrocarbon-containing compound, the molecules of which have both a polar and at least one non-polar region, the hydrocarbon-containing compound containing a cationic surfactant, and the temporary organic Protective cover (3) has an adhesion coefficient µH 0.5 and a sliding friction coefficient µG 0.5 for a counter body made of cotton gauze.

Description

The invention relates to a coated glass pane, in particular for architectural glazing, and a method for its production.

In particular, the invention relates to a coated glass pane for architectural glazing, which is provided for further processing by means of a temperature treatment, in particular for the production of toughened safety glass (ESG) or partially toughened glass (TVG).

Glass panes for use in architectural glazing are often provided with a sequence of several inorganic layers in order to, for. B. to achieve better thermal insulation or to reduce the heating of buildings when exposed to sunlight. Such sun protection and heat protection coatings, also referred to as architectural glass coatings, are known per se and usually comprise one or more metal layers that are so thin that they are still transparent in the visible spectral range. If the architectural glass coating comprises at least one thin metal layer, it is usually embedded between several dielectric layers, in particular oxide or nitride layers, which protect the at least one metal layer in particular from corrosion and reduce reflection in the visible spectral range. Such optically effective layers can be deposited, for example, by means of vacuum coating processes, in particular by magnetron sputtering.

Glass panes, in particular flat glass panes for use as architectural glass, are often thermally pre-stressed by means of a temperature treatment. The essential properties of thermally pre-stressed glass panes are the compressive stresses imposed on the glass by the thermal pre-stressing process, which lead to a significantly increased flexural tensile strength of the glass panes produced in this way compared to untreated glass panes. Thermally toughened glass therefore has a higher mechanical damage threshold than normal float glass. A fully thermally toughened glass pane, so-called toughened safety glass, should generally have a degree of toughening on the surface of at least 69 MPa. Partially toughened glass is generally used when surface compressive stresses of 24 to 52 MPa are reached.

The temperature treatment for the production of thermally toughened glass usually takes place at temperatures of more than 600 ° C. For some years now, coatings have been produced on glass that survive the thermal toughening process. The thermal tempering process is therefore often only carried out after the application of an inorganic layer sequence, which is used, for example, as a sun protection coating or a heat protection coating. Between the coating of the glass pane and the thermal toughening process, the glass pane can go through one or more processing steps, in particular cutting, edge processing, washing or transport.

The different layer materials of coatings for glass panes sometimes have very different properties, in particular different coefficients of thermal expansion. Oxides or nitrides contained in the coatings have only a low tensile strength due to their ceramic nature. Small mechanical damage, e.g. B. hair scratches, can tear open due to the tensile stresses occurring during the temperature treatment to large visible defects. The tensile stresses that occur are greater, the thicker the coating applied to the pane of glass. Temperable architectural glass coatings are more prone to scratching compared to an uncoated glass surface. Scratches can arise in particular when handling the coated glass, e.g. B by touching the pane with rubber gloves or lifting the panes with suction cups. Even with careful processing, scratching cannot always be ruled out.

Coated glass panes, in particular for thermal and sun protection glazing, are usually further processed into multiple pane insulating glass, the coating being oriented towards the interior of the pane of the multiple pane insulating glass and thus being comparatively well protected against corrosion. However, there is a risk that the coating will corrode in the time between the application of the coating and the further processing into a multi-pane insulating glass.

From the pamphlet US 2002/0176988 A1 a temporary protective coating, in particular for a coated glass pane, is known. The publication also describes DE 2351801 A1 the production of a coating on glass objects and the printing DE 69734965 T2 a surface modified layer on top of an anti-reflective layer.

One object of the invention is therefore to provide a coated glass pane and a method for its production, the glass pane being characterized by improved resistance to scratching and / or corrosion and the method being suitable for large-area implementation, in particular due to the low use of material.

This object is achieved by a coated glass pane and a method for its production according to the independent patent claims. Advantageous refinements and developments of the invention are the subject matter of the dependent claims.

A coated glass pane is specified, which is intended in particular for architectural glazing. The glass pane comprises a glass substrate, which can be a pane of float glass, for example. A layer sequence of several inorganic layers is applied to the glass substrate, for example by sputtering, a CVD process or a sol-gel process. The sequence of layers can in particular be provided as a heat protection or sun protection coating.

The layer sequence composed of the inorganic layers can, for example, have none, one or more metal layers and a plurality of dielectric layers. In particular, the layer sequence composed of the inorganic layers can contain one or more metallic functional layers, which preferably contain or consist of silver. The at least one metallic functional layer can, for. B. have a thickness between 5 nm and 20 nm. In the layer sequence, the one or more metallic functional layers are advantageously surrounded by dielectric layers which preferably have oxide, nitride or oxynitride materials. In particular, the dielectric layers can have an oxide, nitride or oxynitride with at least one of the elements Sn, Zn, Ti, Nb, Al or Si. Suitable materials are, for example, SnO ₂ , ZnO, TiO ₂ , Nb ₂ O ₅ , Al ₂ O ₃ , SiO ₂ , AlN, Si ₃ N ₄ or any mixtures of these materials.

A temporary organic protective coating is applied to the sequence of layers made up of the plurality of inorganic layers and functions as a protective layer for the sequence of layers made up of the plurality of inorganic layers. A temporary organic protective coating is understood here and in the following to be a layer which is intended to be removed again before the glass pane is used as intended, for example as a window pane. The temporary organic protective coating can in particular be applied by the manufacturer or coater of the coated glass pane after the layer sequence of the inorganic layers has been applied in order to protect the coated glass pane from mechanical damage and corrosion during further processing steps.

The temporary organic protective coating has a thickness between 0.3 nm and 500 nm. The small thickness of the temporary organic protective coating has the advantage that only a small amount of material is used and therefore the use of material is advantageously low, especially when it is applied to large surfaces such as architectural glass panes.

The temporary organic protective coating is formed from a water-soluble or water-dispersible hydrocarbon-containing compound, the molecules of which each have both a polar and a non-polar functional area. The polar area of the respective molecule has a hydrophilic effect and the non-polar area has a hydrophobic effect. The hydrophilic and preferably charged functional areas of the molecules can adsorb their charges on the surface, while the hydrophobic areas reduce the interaction with the environment, as the hydrophobic areas prevent external forces acting directly on the surface due to their spatial expansion to interact with the inorganic layer sequence. In this way, protection of the inorganic layer sequence from scratches and / or corrosion can already be achieved with a very thin organic protective coating.

The temporary organic protective coating protects the glass substrate provided with the layer sequence of the inorganic layers, for example in at least one of the process steps of cutting the glass pane to size, processing the edges, washing or transporting the coated glass pane. For this purpose, the temporary organic protective coating is only applied temporarily in order to remove it again from the coated glass pane at a later point in time, preferably without leaving any residue.

The temporary organic protective coating advantageously improves the scratch resistance and / or the chemical resistance of the coated glass pane. In particular, the coating is protected from scratches and / or corrosion.

The desired protective effect can be achieved with very thin films that reduce the coefficient of friction of the surface provided with the coating. In the case of mechanical loads, such as can occur when handling the coated glass panes, this means that less shear force is introduced into the layer. This reduces the risk of exceeding the strength limits of the inorganic layer materials, which minimizes the likelihood of scratches occurring.

To reduce friction, it is sometimes sufficient if the temporary organic protective coating consists of only one molecular layer, which does not necessarily have to be closed. The thickness of the temporary organic protective coating can thus advantageously only be between 0.3 nm and 20 nm and preferably only between 0.3 nm and 3 nm. The advantage of these very thin layers is that they have little or no optical interference effect and the change in the reflection color ΔE * of the coated side due to the temporary organic protective coating is no more than ΔE * <1. For the definition of the quantity ΔE *, reference is made to the standard EN ISO 11664-4.

Furthermore, it has been shown that a significantly thicker temporary organic protective coating achieves only a slight improvement in scratch resistance from the point of view of minimizing friction and is not advantageous in particular from an economic point of view.

The temporary organic protective coating has a surfactant. Surfactants represent a suitable class of substances that show self-organizing interfacial activity in highly dilute aqueous solution. Surfactant molecules consist of a polar and thus hydrophilic and at least one non-polar and thus hydrophobic functional area. If the inorganic layer sequence comes into contact with this surfactant liquid, a monolayer of active substance is formed on this wet-chemically, with the hydrophilic and preferably charged functional areas of the molecules on the surface adsorbing their charges, while the hydrophobic parts reduce the interaction with the environment ensure that the hydrophobic areas, due to their spatial expansion, prevent external forces from interacting directly with the surface of the inorganic layer sequence.

According to an advantageous embodiment, the hydrocarbon-containing compound contains or consists of at least one of the following substances: alkanesulfonate, alkylbenzenesulfonate, fatty alcohol sulfate, fatty alcohol polyglycol ether, fatty alcohol ether sulfate, fatty acid methyl ester sulfate, fatty alcohol ethylene glycol, amine oxide, two or more of these substances, imidazoline or pyridine derivatives, or a quaternary mixture of these substances. These substances have the properties described and, due to the Coulomb interaction, can adsorb on the charges on the surface of the inorganic layer sequence.

The hydrocarbon-containing compound of the temporary organic protective coating contains a cationic surfactant. Cationic surfactants with a hydrophilic, positively charged head group and preferably two long hydrophobic alkyl radicals prove to be particularly suitable. Here, one makes use of the property of the surface of the inorganic layer sequence, above a certain pH value, its isoelectric point, to form locally negative charges to which the hydrophilic and positively charged head groups can electrostatically adsorb. The top layer of the inorganic layer sequence can be, for example, an SiO ₂ layer, an Si ₃ N ₄ layer or an SnO ₂ layer. Typical isoelectric points for SiO _{2 are} approximately 1 to 2, while, for example, Si ₃ N _{4 has} an isoelectric point in the range of 6 and SnO _{2 has} an isoelectric point in the range of 4 to 5. In the case of many surfactants, when mixed with preferably deionized water, a pH value greater than 5, preferably greater than 6, is established, which is thus above the isoelectric point of the aforementioned inorganic layers. It is also possible to add substances that influence the pH value to the aqueous surfactant solution and thus to adapt it to the isoelectric point. It is therefore a self-organizing system and typically a closed monolayer of active substance arises on the topmost layer of the inorganic layer sequence.

According to an advantageous embodiment, the temporary organic protective coating contains a cationic surfactant which has no halide as an anion. Cationic surfactants which, instead of a halogen counterion, preferably have anions from the group of methosulphates, ethosulphates, formates or acetates have proven to be particularly advantageous with regard to the undesirable corrosive effect.

Temporary organic protective coatings have proven advantageous which have a quaternary ammonium compound, which does not necessarily have to be cationic, the at least one hydrophobic acrylic, alkyl or alkylbenzene group of which contains at least 10 carbon atoms each. As a result, the spatial distance between an externally acting force and the inorganic layer sequence becomes large enough to shield it advantageously with regard to the introduction of force and thus scratch formation. An example of such a temporary organic protective coating is the cationic surfactant DiOctadecylDiMethylAmmoniumChlorid (DODMAC, DDAC-C18, CAS: 107-64-2). It is a quaternary ammonium salt with a hydrophilic, positively charged head group and two long hydrophobic stearyl Leftovers. The hydrophobic CH chains of the stearyl radical have lengths of 18 carbon atoms, which, due to the spatial distance, make interactions between a foreign body and the surface more difficult. A cationic surfactant with more than just one hydrophobic alkyl group proves to be advantageous because it has the ability to be absorbed by the inorganic Layer sequence is additionally increased and thus supported.

• Dioctadecyldimethylammoniumchlorid, Dioctadecyldimethylammoniummethosulfat, Talgamphopolycarboxyglycinat, Kokosfettiminoglycinat, Kokosfettiminopropionat, Octyliminodipropionat, Kokosdimethylaminoxid, Dimethyl-bis[2-[(1-oxooctadecyl)oxy]ethyl]ammoniumchlorid, Di-hydr. Talgdimethylammoniumchlorid, Ditalgdimethylammoniumchlorid, Dikokodimethylammoniumchlorid, Natriumdioctylsulfosuccinat, Octylglucosid, Hexylglucosid, C8-C10 Alkylglucoside; Gemisch aus kationischen Aminsalzen, 2-Propanol und 2-Butoxy-ethanol; Gemisch aus 2-Butoxy-ethanol, kationisches Fettsäurederivat, Esterquat, Oleylamin, Siloxanen und Silikonen, Talgalkyldi(2-hydroxyethyl)aminoxid und einem pH-Wertregulator; Gemisch aus Ditalgdimethylammoniumchlorid, Oleylaminethoxylat, Talgfett-1,3-diaminopropan, Butylglykol, aminofunktionellem Polysiloxan und einem pH-Wertregulator; Alkyldimethylbenzlyammoniumchlorid, Oleyltripropylentetramin.

With this in mind, the following materials are particularly suitable for the hydrocarbon-containing compound of the temporary organic protective coating:

• Dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium methosulfate, tallow amphopolycarboxyglycinate, coconut fat iminoglycinate, coconut fat iminopropionate, octyliminodipropionate, coconut dimethylamine oxide, dimethyl bis. Tallow dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, dicocodimethyl ammonium chloride, sodium dioctyl sulfosuccinate, octyl glucoside, hexyl glucoside, C8-C10 alkyl glucosides; Mixture of cationic amine salts, 2-propanol and 2-butoxyethanol; Mixture of 2-butoxyethanol, cationic fatty acid derivative, esterquat, oleylamine, siloxanes and silicones, tallow alkyldi (2-hydroxyethyl) amine oxide and a pH regulator; Mixture of ditallow dimethylammonium chloride, oleylamine ethoxylate, tallow-1,3-diaminopropane, butyl glycol, amino-functional polysiloxane and a pH regulator; Alkyldimethylbenzyl ammonium chloride, oleyl tripropylenetetramine.

It is also advantageous if a wax or oil is additionally mixed with the temporary organic protective coating. In particular, one of the following substances can be added to the hydrocarbon-containing compound: carnauba wax, bees wax, polyethylene, polypropylene, paraffin wax, microcrystalline wax, fatty alcohols, oil components from the class of poly (dimethylsiloxanes) or an amino-functional siloxane. Due to their hydrophobic character, these substances in turn form a stable and friction-minimizing film on the hydrophobic areas of the surfactants, which additionally minimizes the likelihood of harmful force input into the inorganic layer sequence and thus supports the effect of the surfactants. In particular, it has been shown that the adhesion of the waxes / oils to the inorganic layer sequence can be improved by surfactants compared to a pure wax / oil emulsion.

The protective effect described so far is particularly advantageous if the inorganic layer sequence represents a thermal insulation layer and / or a sun protection layer, from which, for example, insulating glass for windows or facades is made, since the finest scratches in sunlight can be very annoying here, but mechanical stresses due to the size of the insulating glass of, for example, at least 0.3 m ² , preferably at least 1 m ² up to sizes of 20 m ^2, can hardly be avoided.

According to an advantageous embodiment, the temporary organic protective coating has sufficient adhesion to the inorganic layer sequence in order not to be removed by cleaning with water. For example, the temporary organic protective coating contains surfactant molecules, some of which are initially dissolved and others are dispersed in the aqueous phase. However, the surfactants show good water resistance after adsorption on a surface. In particular, the temporary organic protective coating cannot be removed within 20 seconds by a cleaning process carried out with water at a temperature T <45 ° C. and with brushes, in particular with PE bristles with a diameter of <1 mm. The temporary organic protective coating preferably has sufficient adhesive strength on the inorganic layer sequence so that in particular it cannot be completely removed by a washing machine that is customary on production lines for heat protection or sun protection glass.

The temporary organic protective coating is preferably not peelable from the coated glass pane, as would be the case, for example, in the case of a laminated protective film. This has the advantage that the temporary organic protective film does not have to be mechanically removed and disposed of, and that it is so thin that it does not interfere with further thermal processing.

According to the invention, the protective coating has an adhesion coefficient μ _H 0.5 and a sliding friction coefficient μ _G 0.5 in the case of a counter body made of untreated cotton gauze. Cotton gauze is a material that is used, for example, in gauze bandages that are commonly used in wound care. A reduction in _{static and dynamic friction to µ G} µ _H 0.5, with the inorganic layer sequence having µ _G > 0.5 and µ _H > 0.5 before the protective coating is applied, is advantageous in terms of damaging force input into the inorganic layer sequence. Due to the lower friction, the harmful shear component is reduced when force is applied to the inorganic layer; in particular, the approximation of the coefficient of adhesion and the coefficient of friction to almost identical values is advantageous, as this significantly minimizes the tendency to the stick-slip effect as this is particularly harmful with regard to mechanical damage to the inorganic layer sequence due to the sudden application of shear force.

In a further advantageous embodiment, the temporary organic protective coating has hydrophobic and / or oleophobic properties so that contamination from downstream Processing steps can be removed with little mechanical effort and thus a reduced risk of scratches.

In a further advantageous embodiment, the temporary organic protective coating represents a diffusion barrier for gases and water, which improves the shelf life of the coating.

In a further advantageous embodiment, the inorganic layer sequence is passivated by the temporary organic protective coating and thus the resistance to water and gases is improved.

It is also possible for the glass pane to be coated on both sides.

Furthermore, a method for producing a coated glass pane is specified, which comprises the steps of applying a layer sequence of several inorganic layers by sputtering, a CVD method or a sol-gel method to a glass substrate, and of applying a temporary organic protective coating to the comprises inorganic layer sequence, the thickness of the temporary organic protective coating being between 0.3 nm and 500 nm, preferably between 0.3 nm and 20 nm and particularly preferably between 0.3 nm and 3 nm.

The temporary organic protective coating contains a water-soluble or water-dispersible hydrocarbon-containing compound, the molecules of which have both polar and non-polar functional areas. The water-soluble or water-dispersible hydrocarbon-containing compound is a cationic surfactant. The molecules of the applied temporary organic protective coating adsorb advantageously due to their polar and non-polar regions on the surface of the inorganic layer sequence. In this way the friction is reduced and thus an external force on the inorganic layer system is reduced. The friction is reduced by applying the temporary organic protective coating in such a way that the protective coating has an adhesion coefficient µ _H 0.5 and a sliding friction coefficient µ _G 0.5 for a counter body made of untreated cotton gauze.

Advantageous refinements of the method for producing the coated glass pane emerge from the previous description of the glass pane and vice versa.

The hydrocarbon-containing compound of the temporary organic protective coating preferably contains alkanesulfonate, alkylbenzenesulfonate, fatty alcohol sulfate, fatty alcohol polyglycol ether, fatty alcohol ether sulfate, fatty acid methyl ester sulfate, fatty alcohol ethylene glycol, amine oxides, imidazoline or pyridine derivatives or a quaternary ammonium compound or any mixture of these substances. The hydrocarbon-containing compound is preferably applied from an aqueous solution in concentrations of 0.000001% by weight to 10% by weight and advantageously from 0.0001% by weight to 1% by weight.

In a variant of the method, the temporary organic protective coating is preferably applied to the sequence of layers of the inorganic layers by a spraying process, rolling, printing, brushing, wiping, dipping, spinning, meniscus coating or curtain coating.

In an alternative variant for application from an aqueous solution, thermal evaporation in a vacuum has proven to be advantageous. Due to the lack of an oxygen atmosphere in the vacuum, it is difficult for the vaporized substances to decompose here, which means that materials such as diStearylDiMethylAmmoniumChlorid can also be vaporized in the temperature range from 100 ° C to 250 ° C.

Regardless of the application method, rinsing with preferably demineralized water proves to be advantageous, since inhomogeneities in the temporary organic protective coating can be eliminated. Superfluous material, which does not adsorb directly on the inorganic layer sequence as a monolayer, is preferably rinsed off. This has the advantage that the inorganic layer sequence has a visually appealing appearance even before a subsequent thermal removal of the temporary organic protective coating, and in addition even less material has to be removed, for example by pyrolysis.

In a preferred embodiment of the method, the temporary organic protective coating is dried after application by means of IR radiation and / or a stream of air, which can optionally be heated. This is particularly advantageous when the temporary organic protective coating is applied from an aqueous solution. The temporary organic protective coating can be applied from an aqueous solution under atmospheric pressure. In an advantageous embodiment of the method, the aqueous solution or suspension is removed after application and after formation of the self-organizing temporary organic protective coating by means of an air knife or a stream of warm air. As an alternative, a very thin aqueous solution or suspension can be dried, if necessary by the addition of heat by means of IR radiation or warm air will. The drying is preferably carried out in such a way that the temporary organic protective coating is dry to the touch after less than 2 minutes. This has the advantage that several glass panes can be stacked dry to form a glass joint at the usual production speed.

The temporary organic protective coating is advantageously removed from the inorganic layer sequence after processing and / or transport by means of a temperature treatment. In particular, the temporary organic protective coating can be removed without residue from the inorganic layer sequence by a temperature treatment in which a temperature of at least 600 ° C. is preferably reached. This has the advantage that the temporary organic protective coating does not impair the optical properties of the coated glass pane when used as intended, i.e. after the temporary organic protective coating has been removed.

If residues from the organic layer still remain on the inorganic layer sequence after the temperature treatment, these can optionally be removed with a water-based cleaning process.

In a preferred embodiment of the method, the glass pane is thermally toughened during the temperature treatment with which the temporary organic protective coating is removed from the inorganic layer sequence, wherein the glass pane can be further processed in particular into toughened safety glass or partially toughened glass. This configuration offers the advantage that the temporary organic protective film is removed without residue in the usual production processes in the same step, without the need for an additional work step.

In this advantageous variant of the method, the temporary organic protective coating serves to protect the coated glass pane in the period between the application of the inorganic layer sequence and the final processing of the coated glass pane into thermally toughened glass. This is particularly advantageous if a glass manufacturer or glass coater delivers the already coated glass pane and the final processing into thermally toughened glass only takes place after transport and / or further processing steps at a customer of the glass manufacturer or glass coater.

In a further advantageous embodiment of the method, after the application of the layer sequence from the multiple inorganic layers and before the application of the temporary organic protective coating, optical properties of the glass substrate coated with the layer sequence from the multiple inorganic layers are measured. For example, the transmission and / or the reflection of the coated glass pane are measured. The measurement of the transmission and / or the reflection is advantageously carried out at several points on the glass pane in order to identify any inhomogeneities.

The invention is explained below using exemplary embodiments in connection with the 1 and 2 explained in more detail.

• 1 eine schematische Darstellung eines Querschnitts durch eine beschichtete Glasscheibe gemäß einem Ausführungsbeispiel, und
• 2A bis 2F eine schematische Darstellung eines Verfahrens zur Herstellung der beschichteten Glasscheibe gemäß einem Ausführungsbeispiel anhand von Zwischenschritten.

Show it:

• 1 a schematic representation of a cross section through a coated glass pane according to an embodiment, and
• 2A until 2F a schematic representation of a method for producing the coated glass pane according to an embodiment based on intermediate steps.

Identical or identically acting components are each provided with the same reference symbols in the figures. The components shown and the proportions of the components to one another are not to be regarded as true to scale.

In the 1 Coated glass pane shown schematically in cross section according to an exemplary embodiment has a glass substrate 1 on one layer sequence 2 from several inorganic layers 21 , 22nd , 23 is upset. The coated glass pane can be provided in particular for applications in the field of architectural glazing. The glass substrate 1 is in particular a float glass pane, which has a size of 6 mx 3.21 m, for example.

The inorganic layer sequence 2 can in particular have the function of a heat protection or sun protection coating. Such heat and sun protection coatings are known per se and generally have a large number of individual layers 21 , 22nd , 23 on. The inorganic layer sequence 2 can for example be a base coat 21 , a metallic functional layer 22nd and a top layer 23 exhibit. The base layer 21 and the top layer 23 preferably each have one or more dielectric layers. The base layer 21 and the top layer 23 can in particular each have one or more partial layers of oxides, nitrides or oxynitrides. The cover layer can have SiO _x N _y , for example, or a top sub-layer made of SiO _x N _y .

With the metallic functional layer 22nd that is between the base layer 21 and the top layer 23 is arranged, it is preferably a silver layer, which can, for example, have a thickness of 5 nm to 20 nm. It is also possible that the inorganic layer sequence 2 several metallic functional layers 22nd contains, which are each arranged between dielectric layers. For example, it can be provided that the inorganic layer sequence has two or three metallic functional layers 22nd having.

The coated glass pane described here is based on the inorganic layer sequence 2 advantageously a temporary organic protective coating 3 upset. The temporary organic protective coating 3 is intended as a temporary protective layer during further processing of the coated glass sheet, e.g. B. to protect the coated glass pane during cutting, washing, edge processing or during transport.

The temporary organic protective coating 3 advantageously has a thickness between 0.3 nm and 500 nm, preferably between 0.3 nm and 20 nm and particularly preferably between 0.3 nm and 3 nm. Further advantageous configurations of the coated glass pane result from the exemplary embodiment of a method for producing the coated glass pane described below.

The in 2A The intermediate step shown in the process is the inorganic layer sequence 2 from the several inorganic layers 21 , 22nd , 23 on the glass substrate 1 been applied. The application of the inorganic layer sequence 3 preferably takes place by sputtering, in particular magnetron sputtering. Alternatively, the application can be carried out by a CVD method or a sol-gel method.

As in 2 B shown schematically, in the process, the optical properties of the inorganic layer sequence are advantageously applied before the temporary organic protective coating is applied 2 coated glass substrate 1 measured, for example by means of a spectrometer. For example, the transmission of the layer system for one of a light source 41 emitted light beam 42 with a suitably placed detector 43 be measured. Alternatively, for example, the reflection of the coated glass substrate 1 be measured. The optical properties are preferably measured at at least three points on the coated glass pane. If the glass pane is moved in a transport direction during the coating, the measurement is preferably carried out at at least three points across the transport direction.

After measuring the optical properties of the in 2C shown intermediate step of the organic protective coating 3 on the inorganic layer sequence 2 upset. In one embodiment of the method, the organic protective coating 3 applied from a water-based surfactant solution. Such a surfactant solution can, in particular, be sprayed onto the inorganic layer sequence 2 be applied. For example, an aqueous solution of the substance diStearylDiMethylAmmoniumChlorid, which has a concentration of 0.001 wt .-% and a pH of about 6, is sprayed on, whereby a temporary organic protective coating about 2 nm thick is formed. The spraying can take place, for example, from a distance of approx. 200 mm at an angle of approx. 45 ° against a transport direction in which the glass substrate is located 1 is transported during spraying. In order to achieve rapid drying, the surfactant solution is blown off with the aid of an air knife.

A particularly thin and even surfactant film can be produced by using so-called atomizing spray nozzles, which are dried in a stream of warm air, infrared radiation or a combination of both. A radiator in the wavelength range of> 1 µm is preferably used as the infrared radiator, since water has a high level of absorption in this wavelength range and is thus effectively heated. At the same time, the glass substrate is protected by the preferably IR-reflecting inorganic layer sequence and is therefore only slightly heated.

In a preferred embodiment, a release powder is applied to the temporary organic protective coating before the coated glass panes are stacked 3 upset. This can be done before or after the temporary organic protective coating has dried 3 take place. The separating powder can in particular have spheres made of PMMA. The size of the spheres is preferably at least twice as great as the thickness of the temporary organic protective coating. For example, PMMA spheres with an average diameter of 50 μm can be used. Such PMMA balls are available, for example, under the name Separol G from Aachener Chemische Werke.

As an alternative to applying by means of a spray process, the temporary organic protective coating can be used 3 can also be applied by vacuum deposition. This has the advantage that the exclusion of air prevents the organic compound from burning or degenerating. A preferred method of applying the temporary organic protective coating by means of a vacuum deposition process is thermal vacuum evaporation. DiStearylDiMethylAmmoniumChlorid, for example, is suitable as an evaporable organic material, which can be evaporated in a temperature range from 100 ° C to 250 ° C in a vacuum, since it cannot be decomposed in a vacuum by the influence of oxygen.

The deposition of the organic material of the temporary organic protective coating 3 in a vacuum has the advantage that particularly thin layers can be produced, which do not or not significantly affect the optical function of the inorganic layer system. Unlike the in 2 B In this case, the illustrated method step can be the optical characterization of the inorganic layer sequence 2 advantageously only after the temporary organic protective coating has been applied 3 take place. This avoids the use of a spectrometer system in a vacuum.

After applying the temporary organic protective coating 3 With one of the methods described above, the coated glass pane is further processed, for example. For example, a blank of the coated glass sheet, as in FIG 2D indicated by the dashed lines. Further possible processing steps are e.g. B. washing the coated glass pane, edge processing or transporting the coated glass pane. In these processing steps, the inorganic layer sequence is 2 advantageous due to the temporary organic protective coating 3 protected against mechanical damage, in particular against the formation of scratches, and / or against corrosion.

Before the coated glass pane is used as intended, the temporary organic protective coating is applied 3 , as in 2E shown schematically, preferably by means of a temperature treatment at a temperature of preferably more than 600 ° C. again from the inorganic layer sequence 2 removed.

For the temperature treatment of the coated glass pane, a furnace can be used in particular, which is typically used in the processing of glass into thermally toughened glass such as toughened safety glass (ESG) or partially toughened glass (TVG). The thermal toughening of coated glass panes usually takes place at temperatures of more than 600 ° C, for example around 670 ° C. Removal of the temporary organic protective coating 3 and the thermal toughening of the coated glass pane can therefore advantageously be carried out in a single process step.

The coated glass pane produced in this way has to be used as intended, as in 2F shown, only the glass substrate 1 and the inorganic layer sequence applied thereon 2 on.

The temporary organic protective coating that has been applied in the meantime 3 is preferably residue-free from the inorganic layer sequence due to the temperature treatment 2 been removed.

The coated glass pane can then be further processed into multiple-pane insulating glass, the coated side of the glass pane generally being arranged on an inside of the multiple-pane insulating glass and thus being comparatively well protected from scratches and corrosion. The temporary organic protective coating is therefore no longer required after the coated glass pane has been processed into multi-pane insulating glass and is therefore preferably removed again beforehand in order to avoid any effects on the optical properties, especially in the case of long-term use under the influence of UV radiation and heat such as in the case of architectural glass. The advantages of the temporary organic protective coating consist rather in the protection of the sensitive coating from scratches and corrosion during processing steps between the application of the coating and the final processing of the glass pane to form multiple pane insulating glass.

The invention is not restricted by the description based on the exemplary embodiments. Rather, the invention encompasses every new feature and every combination of features, which in particular includes every combination of features in the patent claims, even if this feature or this combination itself is not explicitly specified in the patent claims or exemplary embodiments.

Claims (18)

Coated glass pane, comprising - a glass substrate (1), - a layer sequence (2) applied to the glass substrate (1) and composed of several inorganic layers (21, 22, 23) and - a temporary organic protective coating (3) having a thickness between 0 , 3 nm and 500 nm, the temporary organic protective coating (3) containing a water-soluble or water-dispersible hydrocarbon-containing compound, the molecules of which have both a polar and at least one non-polar region, the hydrocarbon-containing compound containing a cationic surfactant, and the temporary organic Protective coating (3) has a coefficient of adhesion µ _H ≤ 0.5 and a coefficient of sliding friction µ _G ≤ 0.5 for a counter body made of cotton gauze. Glass pane after Claim 1 , wherein the hydrocarbon-containing compound contains or consists of at least one of the following substances: alkane sulfonate, alkylbenzenesulfonate, fatty alcohol sulfate, fatty alcohol polyglycol ether, fatty alcohol ether sulfate, fatty acid methyl ester sulfate, fatty alcohol ethylene glycol, amine oxide, imidazoline or pyridine derivative, a mixture of two or more of these ammonium compounds. Glass pane after one of the Claims 1 or 2 wherein the cationic surfactant has no halide as an anion. Glass pane after one of the Claims 1 or 2 wherein the hydrocarbon-containing compound comprises a quaternary ammonium compound having at least one hydrophobic acrylic, alkyl or alkylbenzene group containing at least 10 carbon atoms. Glass pane after one of the Claims 1 or 2 , wherein the hydrocarbon-containing compound contains or consists of at least one of the following substances: - Dioctadecyldimethylammonium chloride - Dioctadecyldimethylammonium methosulphate - Tallow amphopolycarboxyglycinate - Coconut fat iminoglycinate - Coconut fat iminopropionate - Oxo-octyl aminodipropionate - coconut oil oxychloride - 1-octyliminodipropionyl-oxo-ammonium-oxo-ammonium-1-octylamine bis-aminopropionate - octylimino-methyl-2-oxo-ammonium chloride - 1-octylimino-methyl-ammonium-oxo hydr. Tallow dimethylammonium chloride - ditallow dimethylammonium chloride - dicocodimethylammonium chloride - sodium dioctyl sulfosuccinate - octyl glucoside - hexyl glucoside - C8-C10 alkyl glucoside - mixture of cationic amine salts, 2-propanol and 2-butoxyethanol, fatty acid, silatoxyethanol, silatoxyethanol, ester, oxivateoxy and ester, silatoxy-olequateoxy-ethanol, ester, oxy-olateoxy-oleic acid, ester, oxy-olateoxy-ethanol, octyl sulfosuccinate, 2-butoxy-olequate-oxy-ethanol, 2-butoxy-olequate-oleic acid, silatoxy-olequate-mixture , Tallow alkyldi (2-hydroxyethyl) amine oxide and a pH regulator - mixture of ditallow dimethylammonium chloride, oleylamine ethoxylate, tallow 1,3-diaminopropane, butyl glycol, aminofunctional polysiloxane and a pH regulator - alkyldimethylbenzlyammonium chloride - oleyltripropylene tetryltrip. Glass pane according to one of the preceding claims, wherein the temporary organic protective coating (3) contains, in addition to the hydrocarbon-containing compound, an admixture of at least one of the following substances: carnauba, bees, polyethylene, polypropylene or paraffin wax, microcrystalline wax, fatty alcohols, Oil component from the class of poly (dimethylsiloxanes), amino-functional siloxane. Glass pane according to one of the preceding claims, wherein the inorganic layer sequence (2) is a thermal insulation layer or a sun protection layer or a combination thereof. Glass pane according to one of the preceding claims, wherein the temporary organic protective coating (3) has sufficient adhesion to the inorganic layer sequence (2) so as not to be removed by cleaning with water. Glass pane according to one of the preceding claims, wherein the temporary organic protective coating (3) does not form a removable film comparable to a foil. A method for producing a coated glass pane, comprising the steps: applying a layer sequence (2) composed of several inorganic layers (21, 22, 23) to a glass substrate (1) by sputtering, a CVD method or a sol-gel coating, and - applying a temporary organic protective coating (3) to the inorganic layer sequence (2), the temporary organic protective coating (3) having a thickness between 0.3 nm and 500 nm, and - the temporary organic protective coating (3) being water-soluble or contains water-dispersible hydrocarbon-containing compound, the molecules of which have both a polar and at least one non-polar region, the hydrocarbon-containing compound containing a cationic surfactant, - the temporary organic protective coating (3) has an adhesion coefficient µ _H ≤ 0.5 and a coefficient of sliding friction µ _G ≤ 0.5 in the case of a counter body made of cotton gauze, and where vo r the application of the temporary organic protective coating (3) µ _H > 0.5 and µ _G > 0.5. Procedure according to Claim 10 , wherein the hydrocarbon-containing compound is applied from an aqueous solution or suspension with a concentration of 0.000001% by weight to 10% by weight of one of the following substances: alkanesulfonate, alkylbenzenesulfonate, fatty alcohol sulfate, fatty alcohol polyglycol ether, fatty alcohol ether sulfate, fatty acid methyl ester sulfate, fatty alcohol ethylene glycol, amine oxide , Imidazoline or pyridine derivative, quaternary ammonium compound, or a mixture of two or more of these substances. Procedure according to Claim 10 or 11 , wherein the temporary organic protective coating (3) through Spraying, rolling, printing, brushing, wiping, dipping, centrifuging, meniscus coating (meniscus coating) or curtain coating (curtain coating) is applied. Procedure according to Claim 10 , wherein the temporary organic protective coating (3) is applied by thermal evaporation in a vacuum. Method according to one of the Claims 10 until 13th , the temporary organic protective coating (3) being rinsed with water. Method according to one of the Claims 10 until 14th , wherein the temporary organic protective coating (3) is dried after application by IR radiation and / or a stream of air, which can optionally be heated. Method according to one of the Claims 10 until 14th , wherein the temporary organic protective coating (3) is removed from the inorganic layer sequence (2) after processing and / or transport of the glass pane (1) by a temperature treatment at at least 600 ° C. Procedure according to Claim 16 , wherein the glass pane is thermally toughened during the temperature treatment, in particular being processed into toughened safety glass or into partially toughened glass. Method according to one of the Claims 10 until 17th , after the application of the layer sequence (2) comprising the plurality of inorganic layers (21, 22, 23) and before the application of the temporary organic protective coating (3), optical properties of the glass substrate (1) coated with the layer sequence (2) are measured.

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